Method of pretreating a sample for X-ray fluorescence analysis

ABSTRACT

A material treating apparatus is used for treating powdery, granular and conglomerate materials. The material treating apparatus includes a material supply apparatus for transferring the materials to a predetermined position, particularly for supplying the materials to an automatic crusher. The material treating apparatus includes a crushing system having a crushing vessel transferring unit. The material treating apparatus further includes an analysis sample transferring apparatus particularly suitable for transferring samples formed by a press to a fluorescent X-ray analyzing apparatus. The material treating apparatus includes a fluorescent X-ray analyzing system which is capable of automatically analyzing samples of various kinds. An analyzing method is carried out by the use of the above material treating apparatus. The analyzing method includes a method of vitrifying an inorganic material, which is preferably used for obtaining samples to be analyzed by the X-ray fluorescence analysis. The analyzing method further includes a method of pretreating samples for the X-ray fluorescence analysis.

BACKGROUND OF THE INVENTION

This invention relates to an apparatus for treating powdery, granularand conglomerate materials and an analyzing method using the apparatus.

In analyzing components of various materials by a method such as theX-ray fluorescence analysis, it is necessary to pretreat the material tobe analyzed.

The following four methods have been known as methods for making samplesof inorganic materials.

(1) A crushing method in which a material is pulverized in order tobring the material into an appropriate condition for the analysis.

(2) A vitrifying method in which a material is added with one or amixture of an alkali metal borate (for example. Li₂ B₄ O₇, Li₂ O.B₂ O₃and Na₂ B₄ O₇) and heated to be vitrified.

(3) An alkali metal carbonate decomposing method in which a material isdecomposed by an alkali metal carbonate.

(4) A decomposition solution method in which a material in a pressurizedvessel is decomposed by a strong acid such as hydrofluoric acid to makeit a solution.

The crushing method, among the above methods, is disadvantageous becauseif the material is at least partially crystalline, the crushed materialstill includes a crystal structure so that analyzed results with highaccuracy could not be obtained in the X-ray fluorescence analysis due tothe socalled "mineral effect". Moreover, it takes a long time to crushinorganic materials including non-oxides as components such as siliconnitride, sialon, silicon carbide and the like owing to high hardness.Moreover, there is a risk that the materials may be contaminated by amaterial of a vessel used for crushing. Therefore, the crushing methodhas been scarcely used other than in cases not requiring a high accuracyof analysis.

The alkali metal carbonate decomposing method is applicable as apretreatment method for wet analyses, even for non-oxides. However, thismethod could not be used for pretreating materials for the X-rayfluorescence analysis due to the fact that decomposed and meltedproducts are high in moisture absorption and are difficult to be removedfrom used vessels such as platinum dishes and the like.

The vitrifying method, using the alkali metal borate, is disadvantageousbecause analyzing accuracy is often lowered since vitrification onlypartially progresses in the case of inorganic materials includingnon-oxides as components.

Moreover, the decomposition solution method using a strong acid requiresa long time (such as 24 hours) for the decompositions. Samples obtainedfor the analysis are liquid which is preferable for the chemicalanalysis. However, it is difficult to use such liquid samples in theX-ray fluorescence analysis because of a limitation of an apparatusitself for the X-ray fluorescence analysis.

The so-called "mineral effect", which means that the grain sizes ofsamples detrimentally affect the accuracy of analysis of the samples,has been known. In order to avoid the mineral effect to carry out theanalysis with high accuracy, it is necessary to pulverize samples inpowdery, granular and conglomerate states into fine powders of the orderof less than 1 μm and to form formed bodes suitable for analysis. It ispreferred that the formed bodies have smooth surfaces for high accuracyanalysis. Moreover, it is desired that the formed bodies are rigid andstable for a long period of time in order to facilitate the operationand automation for the analysis. The crushing to forming processes arereferred to herein as "pretreatment of samples for the X-rayfluorescence analysis".

The pretreating methods for the X-ray fluorescence analysis have beenknown as non-addition dry crushing and non-addition wet crushing methodswhich are carried out in dried and wet conditions without any additions,powdery graphite added dry crushing which is carried out in a driedcondition with added graphite (magazine of Japanese Metallurgy Society,vol. 36, page 648, 1972), and binder added wet crushing which is carriedout in a wet condition with binders such as styrene-maleic acidcopolymer or stearic acid. The powdery graphite has a lubricating effectso that it is effective as a crushing aid for promoting pulverization ofsamples. On the other hand, binders are effective as a forming ormolding aid which gives strength to formed bodies and makes smoothsurfaces of the formed bodies. Graphite is also somewhat effective as amolding aid. However, the effect of graphite as the molding aid isinsufficient for disk-like formed bodies having diameters of more than10 mm which are usually used for the X-ray fluorescence analysis.

Although the above non-addition dry crushing method is simple inoperation, it is disadvantageous since crushing is sometimesinsufficient, analyzing accuracy is lowered due to the mineral effect,and forming samples into disk-like bodies is difficult. The non-additionwet crushing method is disadvantageous since analyzing accuracy islowered, forming samples into disk-like bodies is difficult and,moreover, since volatilization of solvents is needed. The powderygraphite added dry crushing method is disadvantageous since formingsamples into disk-like bodies is difficult, although there is no problemof lowering the analyzing accuracy due to the mineral effect. The binderadded wet crushing method is disadvantageous since there is a problem oflowering the analyzing accuracy due to the mineral effect andvolatilization of solvents is needed. Therefore, a pretreatment methodof samples for X-ray fluorescence analysis has not been proposed,capable of obtaining formed bodies which will bring high accuracyanalysis and are rigid and smooth.

In order to supply powdery, granular or conglomerate materials topredetermined positions such as crushers, weighed materials have beenmanually supplied from hoppers at the predetermined positions toapparatuses such as crushers.

Manual supplying requires skillful operators and obstructs automation ofthe entire installation line. An automated apparatus, for example, ModelHSM-F36 of the HERZOG Company, has been known which comprises, in theproximity of materially supplied positions, a turn table having materialvessels provided along a circumference of the turn table, andintroducing means for intermittently rotating the turn table.

In such an apparatus, however, the material is supplied into the hopperswith the aid of centrifugal forces caused by rotation of the materialvessels driven by the introducing means. Therefore, all the materialscould not be supplied into the hoppers exactly. Moreover, the turn tableis disadvantageous since material is introduced into the hoppers only ina predetermined order due to the fact that the turn table performs itsintermittent rotation only in connection with the material vessels.

Various crushers for crushing samples have been known. With thesecrushers, a crushing operation is carried out with crushing vessels madeof, for example, tungsten carbide (WC) regardless of whether theoperation is manual or automatic.

In this case, introduction of samples and removal of crushed samples areeffected by transferring crushing vessels from the crushers to workingtables. Every time kinds of samples are changed, the crushing vesselsmush also be transferred from the crushers to the cleaning means forcleaning the vessels. These troublesome transferring of the vessels havebeen manually carried out.

The vessels made of tungsten carbide or chromium steel are so heavy thatthe manual operation for transferring the vessels is disadvantageous tosafety and efficiency. On the other hand, when organic binders are addedto samples to be crushed, the binders are likely to stick to inner wallsof the crushing vessels. Therefore, the attached crushed samples couldnot be completely removed from the crushing vessels without manualcleaning.

In various analyzing apparatuses, particularly the fluorescent X-rayanalyzing apparatus, these apparatuses have been supplied with samplesto be analyzed as formed bodies in predetermined shapes or accommodatedin predetermined exclusive holders. In order to make such formed bodiesof samples or insert samples into the holders, separate pressingapparatuses or holder loading and unloading apparatuses are needed.

In this case, the precise X-ray fluorescence analysis for various kindsof samples is accomplished by manually operating the formation of thesamples and transference of the samples to the apparatuses. However itis impossible to automatically supply the samples to fluorescence X-rayanalyzing apparatuses to form automatic analyzing systems. Moreover,when existing holder loading and unloading apparatuses are used, onlyone or two reference samples are held at a time. Therefore, suchexisting apparatuses could not be used for automatically analyzingvarious kinds of samples continuously and precise X-ray fluorescenceanalysis could not be realized, so that the use of the existingapparatuses is limited to particular analyses. Such a limitation of useresults also from the fact that the holders are prohibitively expensiveand particular. Thus, they could not be provided in large quantities.

In order to determine predetermined compositions in samples, the X-rayfluorescence analysis with X-ray has been used and various fluorescentX-ray analyzing apparatuses have been known. With such fluorescent X-rayanalyzing apparatuses, in supplying a sample to the apparatus the samplemust be formed in a predetermined shape and set at a predeterminedposition in a sample holder. Moreover, the sample must be pretreated inorder to avoid the influence of physical and chemical factors of thesample on fluorescence X-ray intensity and to improve the analyzingaccuracy.

For this purpose, in the case of inorganic samples such as ceramics orthe like, it is required to use a crusher for crushing an inorganic rawmaterial into predetermined grain sizes and a press for forming thecrushed material into predetermined shapes. Thus, produced samples areset in the sample holder for the X-ray fluorescence analysis.

With hitherto used apparatuses, introducing the samples into theapparatuses is not reliably effected. Transferring the samples betweenthe apparatuses and setting the samples into the apparatuses must beeffected by skillful operators. Further, even with new systems partiallyautomated with such operations, it might be ineffective, if notimpossible, to carry out various kinds of samples.

SUMMARY OF THE INVENTION

It is a primary object of the invention to provide an apparatus fortreating powdery, granular and conglomerate materials and an analyzingmethod using the apparatus, which eliminate all the disadvantages of theprior art.

It is another object of the invention to provide an improved method forvitrifying inorganic materials, which eliminates all the disadvantagesof the prior art and is preferably used as a method for pretreatingsamples for X-ray fluorescence analysis.

In order to achieve the object, a method of vitrifying an inorganicmaterial according to the invention comprises the steps of: adding aninorganic material with an alkali metal carbonate in an amount which istwice that of the inorganic material in weight, heating the material todecompose it and to obtain a melted product, adding the melted productwith boric acid in an amount which is more than said inorganic materialin weight, and heating the melted product to vitrify it.

In a preferred embodiment, in the step of adding with the alkali metalcarbonate, boric acid is added to the inorganic material, the boric acidbeing 5-50 parts by weight relative to 100 parts by weight of the alkalimetal carbonate and being less than 0.4 mol relative to 1 mole of thealkali metal carbonate.

With the above constitution, an inorganic material to be vitrified isadded with a predetermined amount of an alkali metal carbonate orpreferably, an alkali metal carbonate and boric acid, and decomposed ina heating process. Thereafter, the crystalline substance is vitrified bya predetermined amount of boric acid. Therefore, the mineral effect doesnot occur in X-ray fluorescence analysis and vitrification progressesuniformly so that good samples for analysis can be obtained in a shorttime.

Moreover, the vitrified substance or glass is not moisture absorptiveand is easily peeled from a platinum pan or the like so that it ispreferably supplied for the X-ray fluorescence analysis.

The reason why the alkali metal carbonate is twice the weight of aninorganic material to be vitrified in the decomposing process is that analkali metal carbonate in an amount of less than twice that of theinorganic material makes decomposition of the material insufficient.Moreover, the reason why the boric acid is more in weight than theinorganic material in the vitrifying process is that an amount of boricacid which is less than the inorganic material makes vitrificationinsufficient.

Excess alkali metal carbonate and boric acid in the vitrifying processdo not cause any problem. However, in order to obtain high accuracy inthe X-ray fluorescence analysis, higher X-ray intensity is preferable.For this purpose, preferable upper limits of the alkali metal carbonateis of the order of four times the inorganic material to be vitrified andthe boric acid is of the order of ten times the inorganic material.

Boric acid is preferably 5-50 parts by weight relative to 100 parts byweight of the alkali metal carbonate and is preferably less than 0.4 molrelative to 1 mol of the alkali metal carbonate in the decomposingprocess. The reason for this is that the melted product has aflowability during decomposition so that the melted product can beeasily handled. Addition of boric acid which is less than 5 parts byweight gives only less flowability making handling the melted productdifficult. Addition of boric acid which is more than 50 parts by weightmay cause incomplete decomposition or make the decomposition impossible.

It is a further object of the invention to provide a method ofpretreating samples for the X-ray fluorescence analysis which eliminatesall the disadvantages of the prior art and obtains formed samples whichare rigid and smooth to provide high accuracy analysis, and in which itis easy to automatize its operation and is most suitable for the highaccuracy analysis of various kinds of samples.

In order to achieve this object, the method of pretreating a sample forX-ray florescence analysis according to the invention comprises thesteps of: adding a sample under any powdery, granular and conglomerateconditions with powdery graphite and a forming aid simultaneously or oneafter another, crushing the sample under a dried condition, andpress-forming the sample.

With the above constitution, the sample is added with the powderygraphite and the forming aid simultaneously or one after another, andcrushed under a dried condition, thereby obtaining formed samples madeof crushed materials, which are rigid, smooth and stable for long periodof time. With such samples, high accuracy analysis can be accomplishedby eliminating the influence of the mineral effect on the analysisaccuracy.

In the case that the material is added with powdery graphite and crushedand thereafter added with a forming aid and crushed, crushing isprogressed faster so that the influence of the mineral effect is morereduced. Vibration mills, attrition mills and planetary motion typemills can be preferably used as the crusher. However, the vibrationmills are most preferable because of their high crushing efficiency. Inthe case of using a vibration mill, the crushing time is of the order of8 minutes with simultaneous addition of the graphite and forming aid. Inthe case of addition step by step, the crushing time of 4 minutes perstep is sufficient.

It is a further object of the invention to provide an improved materialsupply apparatus which eliminates all the disadvantages of the prior artand is capable of selectively introducing any materials and introducingmaterials automatically and exactly.

In order to achieve this object, a material supply apparatus accordingto the invention comprises: material vessels for receiving thereinmaterials under any powdery, granular or conglomerate condition,material racks for accommodating therein a plurality of the materialvessels, a material vessel pooling unit for holding the material racksto be driven, a material vessel transferring unit for selecting apredetermined material vessel and taking it out from said material racksand transferring it to a predetermined position, and control means forcontrolling operations of the material vessel pooling unit and thematerial vessel transferring unit.

With this arrangement, the supply of samples is carried out bycontrolling via control means operations of the material vessel poolingunit for driving the material rack accommodating therein sample vesselsand the material vessel transferring unit for selectively transferringthe material vessel, so that any materials can be automatically suppliedin a predetermined order by inputting the predetermined order into thecontrol means.

In the case that the material vessel transferring unit comprises: thegrasping means, the lifter, the transfer means and the turn-overintroducing means, after positioning the material vessel into apredetermined position by the grasping means, the lifter and thetransfer means, the material in the vessel is completely supplied by theturn-over introducing means, thereby supplying the material moreexactly.

It is an object of the invention to provide a crushing system having acrushing vessel transferring unit which eliminates all the disadvantagesof the prior art, and automatizes the transference of heavy crushingvessels without automatizing manual operations such as cleaningoperations which require parts.

In order to achieve this object, the crushing system having a crushingvessel transferring unit according to the invention comprises a crusherfor crushing a sample in a crushing vessel, a working table forintroducing the sample into the crushing vessel and removing a crushedsample from the crushing vessel, a crushing vessel cleaning unit forcleaning the crushing vessel from which the crushed sample has beenremoved, a crushing vessel stocker for storing cleaned crushing vessels,and a crushing vessel transferring unit for transferring the crushingvessels between the manual crusher, the working table, the crushingvessel cleaning unit and the crushing vessel stocker.

With the above arrangement, the crushing vessels are transferred betweenthe crusher, working table, cleaning unit and stocker by means of thecrushing vessel transferring unit, the introduction and removal ofsamples and cleaning are manually effected, while heavy crushing vesselsare automatically transferred, so that crushing of samples can becarried out safely with high efficiency.

Moreover, the crushing vessel transferring unit comprises: a traversefeeding mechanism capable of coarse movements and fine movements forpositioning, a lifting mechanism for raising and lowering the crushingvessels, a clamping mechanism for clamping the crushing vessel, atilting mechanism for tilting the crushing vessel, and a control boardfor instructing operations of the above mechanisms. Therefore, thetraverse feeding mechanism capable of rough and fine movements enablesthe crushing vessels to be exactly positioned at the crusher, workingtable, cleaning bath and turn table. The crushing vessel clamped in theclamping mechanism can be tilted during cleaning by the tiltingmechanism, so that the crushing vessel is cleaned by both hands of anoperator, thereby shortening the time required for cleaning andeffecting the cleaning with high efficiency.

It is another object of the invention to provide an improved analysissample transferring apparatus which eliminates all the disadvantages ofthe prior art and which enables a system to be automatized andpreferably supplies various kinds of samples successively to ananalyzing apparatus.

It is a further object of the invention to provide an analysis sampletransferring apparatus which is inexpensive and does not detrimentallyaffect the accuracy of X-ray fluorescence analysis by providing a holderwith clamp means which is a modification of existing clamp means.

For this object, the analysis sample transferring apparatus according tothe invention comprises: a formed sample transferring unit fortransferring and temporarily storing formed samples, a formed sampleloading and unloading unit for loading and unloading a formed sampleinto and out of a predetermined holder and loading and unloading theloaded and unloaded holder into and out of a holder tray, a formedsample delivery unit for transferring the formed samples between theformed sample transferring unit and the formed sample loading andunloading unit, a holder tray transferring unit for transferring theholder tray to a predetermined position, and a reference sample storingand lifting unit.

With the above arrangement, a formed analysis sample can be loaded intoand unloaded out of the holder in a predetermined timing, and the holdercan be transferred to a predetermined analyzing apparatus by the holdertray, so that the analysis sample can be automatically transferred tothe predetermined analyzing apparatus without requiring manualoperations. Moreover, a reference sample storing and lifting unitcapable of storing various kinds of reference samples is added to theholder tray transferring unit, calibration curves or calibration ofanalyzing apparatus during the analysis of various kinds of samples.Further, formed samples can be loaded into and unloaded out of theholder, so that samples of various kinds are analyzed with highaccuracy.

It is an object of the invention to provide a fluorescent X-rayanalyzing system which eliminates all the disadvantages of the prior artand which is capable of handling samples of various kinds and does notrequire any manual operation for transferring samples between respectiveunits and for setting the samples in the respective units so that manualoperations can be completely deleted.

For the object, the fluorescent X-ray analyzing system according to theinvention comprises: an automatic crusher for selecting a predeterminedsample from various samples and crushing the sample into a predeterminedsize, a crushed sample transferring unit for transferring the crushedsample, an automatic press for forming the sample transferred by thecrushed sample transferring unit into a predetermined shape, a formedsample supply unit for supplying the formed sample to a next step, afluorescent X-ray analyzing apparatus for determining amounts ofelements in the supplied sample, and control means for controllingrespective operations of the automatic crusher, the crushed sampletransferring unit, the automatic press, the formed sample supply unitand the fluorescent X-ray analyzing apparatus.

With the above arrangement, the crushed sample transferring unit and theformed sample supply unit connect between the automatic crusher,automatic press and fluorescent X-ray analyzing apparatus, andoperations of these components are controlled by the control means.Therefore, automatization of the system can be accomplished and powercan be saved.

Moreover, samples of various kinds are continuously automaticallyanalyzed without contamination between the samples by the use of theautomatic crusher for selectively crushing the samples of various kinds,preferably comprising the sample rack, sample supply unit and cleaningunit and securely cleaning the crushing vessel.

Further, when the fluorescent X-ray analyzing apparatus comprises thesample transferring unit, the holder loading and unloading unit and thesample loader, the formed samples are automatically supplied to thefluorescent X-ray analyzing apparatus in a preferable manner.

In order that the invention may be more clearly understood, preferredembodiments will be described, by way of example, with reference to theaccompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plan view illustrating one example of a material supplyapparatus according to the invention together with an automatic crusher;

FIG. 2 is a front elevation illustrating the material supply apparatusand the automatic crusher shown in FIG. 1;

FIG. 3 is a front elevation of a material vessel transferring unit inthe material supply apparatus shown in FIG. 1;

FIG. 4 is a side view of the material vessel transferring unit;

FIG. 5 is a plan view illustrating one example of a crushing systemaccording to the invention;

FIG. 6 is a front elevation of the crushing system as shown in FIG. 5;

FIG. 7 is a schematic view for explaining a clamping method for acrushing vessel;

FIGS. 8a and 8b are side and plan views illustrating a cover and acrushing vessel for the crushing system, which is provided with safetydevices for the operation;

FIG. 9 is a plan view illustrating one example of an analysis sampletransferring unit according to the invention together with a fluorescentX-ray analyzing apparatus;

FIG. 10 is a front elevation illustrating the analysis sampletransferring unit and the analyzing apparatus shown in FIG. 9;

FIG. 11a is a sectional view of a holder to be used in the analysissample transferring unit shown in FIG. 9;

FIG. 11b is a bottom plan view of the holder shown in FIG. 11a;

FIG. 11c is a sectional view of a clamp built-in spindle used in theanalysis sample transferring unit shown in FIG. 9;

FIG. 12 is a plan view illustrating one example of a fluorescent X-rayanalyzing system;

FIG. 13 is a plan view illustrating one example of an upper constructionof an automatic crusher used in the system shown in FIG. 12; and

FIG. 14 is a side view of the upper construction of the automaticcrusher shown in FIG. 13.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The vitrifying method for preparing samples to be analyzed according tothe invention will be explained as one example hereinafter referring toa case that an inorganic material including silicon nitride is theinorganic material to be vitrified. The inorganic material includingsilicon nitride is referred to hereinafter simply as "silicon nitride".First, powder of the silicon nitride or coarse grains of sinteredsilicon nitride (for example 3 mm, 5 mm and the like) are prepared byweighing. Lithium carbonate or the like as an alkali metal carbonate,and boric acid if required are prepared by weighing. The preparedsilicon nitride, lithium carbonate and boric acid are mixed in a dishmade of platinum-gold alloy and then progressively heated by a Bunsenburner and, if required, a Meker burner. In this case, the heating isstarted from a low temperature and the heating power is progressivelyincreased to effect a decomposition resulting from the heating. Such aheating and decomposing process is completed at an instant when bubblesof CO₂, N₂ and the like generating from the mixture disappear.

After the mixture is cooled by leaving it in the atmosphere, the mixtureis added with a predetermined amount of boric acid and heated by theMeker burner. The heating is started from low temperature and theheating power is progressively increased. At the last stage of theheating, the mixture is intensively heated at about 1,000° C. to achievevitrification of the mixture. In the vitrifying process, the meltedmixture is intensively heated while the mixture is rocked. After thevitrification, compressed air is jetted onto the dish of theplatinum-gold alloy to forcedly cool the mixture. Thereafter, the meltedmixture is stripped from the dish. In order to prevent the detrimentalinfluence by segregation of the vitrified products, the melted productsare pressed after grinding to obtain formed bodies for the X-rayfluorescence analysis. It takes about two hours from time of thepreparation of the sample to the X-ray fluorescence analysis.

If required, sodium carbonate or potassium carbonate may be used as themetal carbonate instead of the lithium carbonate. Moreover, other dishesmay be used such as a crucible made of platinum-gold alloy, platinum,graphite or a dish of platinum. Actual examples will be explainedhereinafter.

In order to carry out the vitrifying method according to the invention,silicon nitride samples No. 1-7 were prepared which were different inthe amount of silicon nitride they contained and included lithiumcarbonate and boric acid of the respective percentages shown in Table 1.Decomposing states in the heating and decomposing process and vitrifiedstates in the vitrified process were reviewed. Those which werecompletely decomposed and whose glasses were transparent and easilystripped are indicated by ⊚. Although completely decomposed and glasssamples were easily stripped, those which were somewhat difficult to bestripped are indicated by ○. Those which were incompletely decomposedand vitrified are indicated by X in Table 1.

                                      TABLE 1                                     __________________________________________________________________________              Silicon                                                                           Percentage                                                                nitride                                                                           of silicon                                                                          Lithium                                                                             Boric acid (g)                                                                            Estimate                                          sample                                                                            nitride                                                                             carbonate                                                                           When   When Decomposi-                                                                          Vitrifi-                                 No.                                                                              (g) (wt %)                                                                              (g)   decomposed                                                                           vitrified                                                                          tion  cation                            __________________________________________________________________________    Present                                                                              1  2   90    4.0   0      2    ○                                                                            ○                          invention                                                                            2  2   85    4.0   0.2    2    ○                                                                            ○                                 3  2   90    5.0   0.5    5    ⊚                                                                    ⊚                         4  2   99    5.0   0.5    10   ⊚                                                                    ⊚                         5  2   75    8.0   2.0    20   ⊚                                                                    ⊚                         6  2   55    5.0   2.5    5    ○                                                                            ○                                 7  2   30    4.0   0.2    2    ○                                                                            ○                          Comparative                                                                          8  2   80    2.0   0.2    2    X     X                                 example                                                                              9  2   90    5.0   0.5    1    ⊚                                                                    X                                        10 2   90    2.0   0.2    1    X     X                                        11 2   80    2.0   2.0    2    X     X                                 __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________              Silicon                                                                           Percentage                                                                carbide                                                                           of silicon                                                                          Lithium                                                                             Boric acid (g)                                                                            Estimate                                          sample                                                                            carbide                                                                             carbonate                                                                           When   When Decomposi-                                                                          Vitrifi-                                 No.                                                                              (g) (wt %)                                                                              (g)   decomposed                                                                           vitrified                                                                          tion  cation                            __________________________________________________________________________    Present                                                                              21 2   90    4.0   0      2    ○                                                                            ○                          invention                                                                            22 2   85    4.0   0.2    2    ○                                                                            ○                                 23 2   98    5.0   0.5    5    ⊚                                                                    ⊚                         24 2   80    5.0   0.5    10   ⊚                                                                    ⊚                         25 2   55    5.0   2.5    5    ○                                                                            ○                                 26 2   30    4.0   0.2    2    ○                                                                            ○                          Comparative                                                                          27 2   90    2.0   0.2    2    X     X                                 example                                                                              28 2   95    5.0   0.5    1    ⊚                                                                    X                                        29 2   95    2.0   2.0    2    X     X                                 __________________________________________________________________________

Moreover, silicon carbide samples Nos. 21-26 were prepared and testedwhich were different in the amount of silicon carbide they contained.Results are shown in Table 2, which are estimated in the same manner asin Table 1. Among these samples, the silicon nitride sample No. 4 andthe silicon carbide sample No. 23 are powdery raw material, while theother samples are coarse grains of sintered materials.

Silicon nitride samples Nos. 8-11 and silicon carbide samples Nos. 27-29were separately prepared and included lithium carbonate or boric acidwhose amounts were out of the range according to the invention. Thesecomparative samples were vitrified. With the silicon nitride samplesNos. 1-11 and the silicon carbide samples Nos. 21-29, the respective tensamples were vitrified and estimated.

As can be seen from the results in Tables 1 and 2, the samples Nos. 1-7and Nos. 21-26 are substantially good in decomposition andvitrification. Amounts of lithium carbonate in the heating anddecomposing processes in these samples are more than twice that of thesilicon nitride samples or silicon carbide samples. Amounts of boricacid in the vitrifying processes in these samples are equal to or morethan those of the silicon nitride samples or silicon carbide samplesaccording to the invention. On the other hand, decomposition andvitrification are insufficient with the comparative samples Nos. 8-11and Nos. 27-29 which do not fulfil the above conditions according to theinvention.

Moreover, ten samples were prepared by crushing sintered silicon nitridewithout vitrification. Further, ten samples were prepared by crushingafter vitrification according to the manner as in sample No. 3 in Table1 of the invention. These samples were subjected to the X-rayfluorescence analysis to review calibration curves (relations betweenintensities of X-ray fluorescence analysis and concentrations of therespective components).

Table 3 indicates accuracies of the calibration curves of the respectivecomponents with the aid of the following equation: ##EQU1##

Moreover, accuracies of calibration curves with silicon carbide crystalswere measured in the same manner as described above, the results ofwhich are shown in Table 4. In both cases of silicon nitride and siliconcarbide, accuracies of analyzed values by the X-ray fluorescenceanalysis with samples vitrified according to the invention are onefigure or place higher than those with samples crushed without beingvitrified.

                  TABLE 3                                                         ______________________________________                                                                 Without                                                         With vitrification                                                                          vitrification                                        Analyzed   (third embodiment)                                                                          (crushing method)                                    component  (wt %)        (wt %)                                               ______________________________________                                        Si         0.04          0.8                                                  Al         0.008         0.05                                                 Fe         0.02          0.02                                                 Ti         0.002         0.002                                                Ca         0.001         0.001                                                Mg         0.02          0.1                                                  K          0.002         0.002                                                Na         0.002         0.002                                                Sr         0.01          0.1                                                  Ce         0.02          0.3                                                  Zr         0.02          0.4                                                  Y          0.02          0.6                                                  ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                                 Without                                                                       vitrification                                        Analyzed   With vitrification                                                                          (crushing method)                                    component  (wt %)        (wt %)                                               ______________________________________                                        Si         0.04          0.9                                                  Al         0.002         0.03                                                 Fe         0.01          0.01                                                 Ti         0.002         0.002                                                Cr         0.008         0.009                                                ______________________________________                                    

The invention is not limited to the embodiments described above andvarious changes and modifications may be made in the invention. Forexample, although the above embodiments have been explained with siliconnitride and silicon carbide, the invention is applicable to usualinorganic materials such as sintered ceramics, glasses, powders and thelike. Moreover, although the above embodiments have been explained inconsideration of the X-ray fluorescence analysis, it is possible to usethem as samples for a wet analysis such as atomic absorptionspectrometry, inductively coupled plasma atomic emission analysis andthe like by solving vitrified products or their crushed materials in anacid.

As can be seen from the above explanation, an inorganic material isadded with a predetermined amount of alkali metal carbonate, preferablyalkali metal carbonate and boric acid and decomposed in the heating anddecomposing process. Thereafter, the mixture is vitrified with apredetermined amount of boric acid. Therefore, when the sample isanalyzed by the X-ray fluorescence analysis, no mineral effect occurs sothat high accuracy analysis can be effected in comparison with thecrushing method. In the X-ray fluorescence analysis using samplesvitrified according to the invention, the time required for the analysiscan be shortened to about one tenth of that in the chemical analysis.

The inorganic material vitrifying method according to the invention isadvantageously used for producing or pretreating samples for the X-rayfluorescence analysis as a high speed analysis so that the industrialvalue of the invention is inestimable.

A method of pretreating samples or specimens to be analyzed according tothe method of the invention will be explained hereinafter. However,samples or specimens to be analyzed according to the method of theinvention may be, of course, pretreated by any other methods explainedherein. An actual embodiment will be explained.

A granular feldspar specimen having sides less than 10 mm, powderygraphite and styrene-maleic acid copolymer were prepared and weighed toobtain compositions shown in Table 4. Thereafter, the weighed granularfeldspar specimen, powdery graphite and styrene-maleic acid copolymerwere simultaneously introduced into a vessel made of tungsten carbideand crushed or pulverized in a dried condition by the use of a vibratingmill for about eight minutes. Then the crushed materials were pressed indies as material holding means or without dies at a forming pressure of30 tons to obtain disk-like formed bodies 38 mm in diameter to beanalyzed by the X-ray fluorescence analysis.

At the same time, disk-like formed bodies were prepared in the samemanner described above with the exception of the addition of the powderygraphite as comparison samples. Moreover, other formed bodies wereprepared as samples of the prior art, in which the powdery graphite wasadded without adding the styrene-maleic acid copolymer. In other formedbodies as samples of the prior art, crushing was effected without addingthe powdery graphite.

The material or formed body holding means were rings or cups forreceiving the formed bodies in order to facilitate the forming operationand handling of the bodies which were poor in moldability.

Steel rings, synthetic resin rings, aluminum rings, aluminum cups andthe like are preferably used for this purpose. However, the steel ringsare the most preferable because they are able to be repeatedly used andto retain deformation of the formed bodies to less extent.

Although the diameters of the formed bodies are 38 mm in the aboveembodiment, the diameters are not limited to this value. For example, ifthe amounts of samples are small, dies having smaller diameters may beused to obtain smaller diameter formed bodies. Formed bodies havingsmall diameters of the order of 10 mm can be supplied to the X-rayfluorescence analysis according to the invention.

Although a forming pressure of 30 tons (about 2.6 ton/cm²) are used inthe above embodiment, the forming pressure is not limited to this value.The forming pressure requires only to be able to give the formed bodiesthe strength sufficient to be supplied to the X-ray fluorescenceanalysis and is preferably 0.2-5 ton/cm².

The formed bodies obtained were compared with states of the bodies andmeasured accuracies of SiO₂ calibration curves by X-ray fluorescenceanalysis. The states of the formed bodies were classified as follows:those designated by ⊚ which were strong, superior in surface smoothnessand very stable for long periods of time, those designated by ○ whichdid not have cracks but were not very good in surface smoothness or lessstable for long periods, those designated by Δ which were poor inaccuracy owing to partial cracks but were able to be analyzed by theX-ray fluorescence analysis, and those designated by X which were notobtained in formed bodies. The accuracies σ of calibration curves wereobtained by using reference samples according to the equation (1)described above. The results are shown in Table 5.

                                      TABLE 5                                     __________________________________________________________________________                                             Compar-                                                                       ative                                                                         example                                                                            Prior art                                                                Crushed          Crushed                                                      in dry           in dry                                                       with Crushed in dry                                                                            with                            Present invention            binder                                                                             graphite    binder              Sample No.  1  2   3    4   5   6    7   11   12 13   14  15                  __________________________________________________________________________    Amount of feldspar                                                                        5.0                                                                              5.0 5.0  5.0 5.0 5.0  5.0 5.0  5.0                                                                              5.0  5.0 5.0                 sample (g)                                                                    Added amount of                                                                           0.25                                                                             0.25                                                                              0.5  1.0 1.5 2.0  2.0 --   0.5                                                                              1.0  1.5 --                  graphite (g)                                                                  Percentage to sample                                                                      1  5   10   20  30  40   40  --   10 20   30  --                  (wt %)                                                                        Styrene-maleic acid                                                                       0.25                                                                             0.5 1.0  1.0 1.5 1.5  2.0 0.5  -- --   --  0.5                 copolymer (g)                                                                 Percentage to sample                                                                      5  10  20   20  30  30   40  10   -- --   --  10                  (wt %)                                                                        Formed body Steel                                                                            With-                                                                             With-                                                                              With-                                                                             With-                                                                             With-                                                                              With-                                                                             Without                                                                            Steel                                                                            Alumi-                                                                             Alumi-                                                                            Without             supporting means                                                                          ring                                                                             out out  out out out  out using                                                                              ring                                                                             num  num using                              using                                                                             using                                                                              using                                                                             using                                                                             using                                                                              using       ring cup                     State of formed body                                                                      ○                                                                         ⊚                                                                  ⊚                                                                   ⊚                                                                  ⊚                                                                  ⊚                                                                   ⊚                                                                  ○                                                                           X  X    Δ                                                                           ○            Accuracy of SiO.sub.2                                                                     0.11                                                                             0.017                                                                             0.027                                                                              0.046                                                                             0.034                                                                             0.25 0.29                                                                              0.55 -- --   0.32                                                                              0.36                calibration σ wt %                                                      (Determination range                                                          (50-85 wt %)                                                                  __________________________________________________________________________

As can be seen from the results of Table 5, the samples subjected to thepretreatment according to the invention are superior in the state offormed bodies and make it possible to carry out correct measurements.

Moreover, the same measurement was effected with other silicates. It hasbeen found that the pretreatment method can be applicable to almost allthe silicates. They are pulverized to average grain diameters of about0.5 μm in a few minutes and disk-like formed bodies under goodconditions are easily obtained.

As can be seen from the above explanation, the mineral effect of samplesis remarkably reduced to make the analysis with high accuracy by addingthe forming aid such as powdery graphite and styrene-maleic acidcopolymer to the sample simultaneously or one after another and crushingthem in a dried condition. Moreover, as the samples are crushed in adried condition according to the invention, the preparation of samplesis completed in a short period of time. Furthermore, a suitable formedbody holding means makes it easy for automatically handling the formedbodies so that all the operations of the X-ray fluorescence analysis,including the pretreatment, can be automated with ease.

FIGS. 1 and 2 illustrate in plan and front views one example of thematerial supply apparatus according to the invention.

In this embodiment, above an automatic crusher 1 and on a base 5 amaterial supply unit 4 is provided comprising a material vessel poolingunit 2 and a material vessel transferring unit 3 so that particularmaterials are selected from various kinds of materials and introducedinto the automatic crusher 1. Material racks 6-1 to 6-8 of the materialvessel pooling unit 2 receive ten material vessels 7, respectively.There are totally 8×10) material vessels 7. Before starting theoperation, positions and kinds of the eighty materials are inputted intoa control means 8, on the basis of which inputted data the materials aresupplied. The material vessel pooling unit 2 is able to move in bothdirections shown by an arrow so that a rack or rack 6-1 in thisembodiment positioned at a rack moving position, a, is transferred to amaterial introducing position shown in the drawing. The materials in thematerial vessels 7 at the material introducing position are held andtransferred by the material supply unit 4 in a predetermined order so asto be supplied into a material introducing opening of the automaticcrusher 1.

FIGS. 3 and 4 illustrate in front and side views one example of thematerial vessel transferring unit 3 of the material supply unit. In theembodiment shown in FIGS. 3 and 4, the material vessel transferring unit4 comprises grasping means 11, a lifter 16, transfer means 21 andturn-over introducing means 26. The grasping means 11 embraces and holdsthe material vessel 7 by supports 12-1 and 12-2 on both sides. Thelifter 16 raises and lowers the material vessel 7, embraced by thegrasping means 11. The lifter 16 is raised or lowered by a motor 18which dries ball screws 17 to raise or lower nuts 19 engaged with theball screws 17. The transfer means 21 translately moves, relative to thebase 5, along guides provided on the base 5. The turn-over introducingmeans 26 comprises a turn-over mechanism 27 for turning over theembraced material vessel by 180°, and an introducing mechanism 28 forstriking a bottom of the material vessel 7 once or twice to remove thecongregated material at the inside of the bottom from the vessel.

The material vessel transferring unit 3 described above is moved by thetransfer means 21 to a position of the predetermined material vessel 7in the material rack 6-1 at the material introducing position. Then thematerial vessel transferring unit 3 is lowered to the position of thematerial vessel 7 where the vessel 7 is embraced by the grasping means11. The material vessel transferring unit 3 is then once raisedembracing the vessel 7 by the lifter 16. Thereafter, the transferringunit 3 is transferred by the transfer means 21 to the materialintroducing port of the automatic crusher 1. From this position, theunit 3 is lowered by the lifter 16 to the proximity of the materialintroducing port, and thereafter the unit 3 is turned over through 180°by the turn-over mechanism 27 of the turn-over introducing means 26.Finally, the introducing mechanism 28 strikes once or twice the bottomof the material vessel 7 to supply the remaining congregated material atthe inside of the bottom into the material introducing port. Thematerial supplying operation is completed in this manner. Moreover, allthe operations above described are effected by control of the controlmeans 8.

As can be seen from the above explanation, the material supply apparatussupplies material by controlling the operations of the material vesselpooling unit and the material vessel transferring unit by the controlmeans. Therefore, a predetermined order of the operations is previouslyinputted in the control means so that desired materials can beselectively introduced into a required apparatus. Moreover, theintroduction of the material can be effected automatically and exactly.

FIGS. 5 and 6 are plan and front views illustrating one example of thecrushing system having a crushing vessel transferring unit according tothe invention. In this embodiment, the crushing system comprises on abase 91 a manual crusher 41, a working table 51, a crushing vesselcleaning unit 61, a crushing vessel stocker 71 and the crushing vesseltransferring unit 81.

The manual crusher 41 is commercially available in this embodiment.After a crushing vessel 42 holding samples to be crushed therein hasbeen arranged at a predetermined position in the manual crusher 41, thecrusher 41 is closed by a cover 43 and the vessel 42 therein isrestrained by an air bag (not shown). Thereafter, the crusher isvibrated by rotation of a motor to crush the samples in the vessels inthe crusher. Loading of the crushing vessel 42 into the crusher 41 iscarried out by the use of the crushing vessel transferring unit 81.

With the manual crusher 41 in this embodiment are particular safetydevices associated with the cover 43. Referring to FIGS. 8a and 8billustrating the cover 43 and the crushing vessel 42, respectively, infront and plan views. The cover 43 is manually opened by one hand of anoperator gripping a grip 92. In this case, the cover 43 is slowly movedby an action of a hydraulic shock damper 93. When the cover approachesthe vessel 42, a cover support mechanism 94 butts against the vessel 42so that the closing of the cover 43 is prevented. Therefore, theoperator grips a lever by his other hand and pushes the lever as shownby an arrow in FIG. 8b to disengage the cover support mechanism 94 fromthe engagement with the vessel 42. In order to close the cover, it isabsolutely necessary for the operator to manipulate the grip 92 by onehand and lever 95 by another hand so that the operator does notunintentionally clamp his hand between the cover 43 and vessel 42.Therefore, the hydraulic shock damper and the cover support mechanism 44having the lever 95 form a safety device for the operation. Moreover,the cover 43 is provided with a microswitch 96 such as a contactlessswitch. When the cover 43 is completely closed, the microswitch 96causes a power source for the crushing vessel 42 to turn on so that thecrushing vessel 42 starts to operate after closing the cover 43 withoutfail. Such a microswitch 96 also forms a safety device.

On the working table 51 is arranged the crushing vessel 42 which hasbeen clamped by the crushing vessel transferring unit 81 and transferredfrom the manual crusher 41 or crushing vessel cleaning unit 61. For thispurpose, a height of the table 51 is substantially equal to heights ofthe manual crusher 41 and the crushing vessel cleaning unit 61.

The crushing vessel cleaning unit 61 used for washing and cleaning thecrushing vessels 42 is constructed for this purpose such that thecrushing vessel 42, held by the crushing vessel transferring unit 81, iscleaned by water and alcohol in a scullery or sink 62 made of stainlesssteel. In other words, the crushing vessel 42 which has been transferredthereto by the crushing vessel transferring crusher 41 is arranged inthe scullery or sink 62 wherein the vessel 42 is cleaned with water bynylon scrubbing brushes or the like and washed with alcohol, therebyremoving from the inside of the vessel 42 samples crushed in previouscrushing processes which remain in the vessel 42.

The crushing vessel stocker 71 is used to dry the cleaned vessels 42arranged thereon to prepare the vessels 42 for the next use. The stocker71 comprises a manually rotatable turn-table 72 on which five crushingvessels 42 are held. Positioning of the turn-table 72 in its manualrotation is effected by click stops corresponding to five vessel holder73-1 to 73-5.

The crushing vessel transferring unit 81 moves together with thecrushing vessel 42 held thereby between the manual crusher 41, theworking table 51 and the crushing vessel cleaning unit 61. The crushingvessel transferring unit 81 in this embodiment comprises: a traversefeeding mechanism 82 capable of rough movements and fine movements forpositioning, a lifting mechanism 83 for raising and lowering thecrushing vessel 42, a clamping mechanism 84 for clamping the crushingvessel 42, a tilting mechanism 85 for tilting the crushing vessel 42,and a control board 86 for instructing and controlling operations of thetraverse feeding mechanism 82, lifting mechanism 83 and tiltingmechanism 85.

The traverse feeding mechanism 82 is so constructed as to enable thecrushing vessel 42 to move in a rough movement to a desired position orthe proximity of the desired position with the aid of an electric motoraccording to an instruction by pushing a switch of the control board 86.Moreover, the traverse feeding mechanism 82 is so constructed that afterthe rough movement, the crushing vessel 42 is manually moved in a finemovement to achieve an exact positioning of the vessel 42 in a case asthe crushing vessel 42 is loaded into the manual crushing vessel 41 andcrushing vessel stocker 71. The lifting mechanism 83 serves to raise orlower the crushing vessel 42 which has been transferred to the desiredtransferred position by operation of a switch of the control board,thereby moving the crushing vessel to or from a predetermined position.When the crushing vessel 42 is raised to the uppermost position orlowered to the lowermost position in the scullery 62 of the crushingvessel cleaning unit 61, the raising or lowering movement is stopped bya limit switch (not shown) for the upper or lower limit. The clampingmechanism 84 is constructed such that by rotating a clamping wheel 87,clamp levers 48 are adjusted to clamp the crushing vessel 42 securely.There are two kinds of crushing vessels 42 according to amounts ofsamples to be crushed in this embodiment shown in FIG. 7. The clamplevers 88 are formed in their insides with grooves 89. In the case of asmaller crushing vessel 42, as shown on the left in FIG. 7, the vessel42 is clamped by the insides of the clamp levers 88 except the grooves89. On the other hand, a larger crushing vessel 42, as shown on theright in FIG. 7, is clamped by the inside of the grooves 89 of the clamplevers 88. Therefore, one kind of clamp levers can clamp two kinds ofcrushing vessels in this manner. The tilting mechanism 85 serves to tiltthe crushing vessel 42 to assist the cleaning operation by water. Thecrushing vessel 42 can be tilted at any angle by rotating a tiltingwheel 90 which is preferably made of stainless steel, resistant to rust.

The invention is not limited to the embodiment and various changes andmodification may be made in the invention. For example, although thefive crushing vessels have been held on the turn-table 32, many vesselsmore than five may, of course, be held on the table.

As can be seen from the above explanation, according to the crushingsystem having the crushing vessel transferring unit of the invention,the transference of the crushing vessels between the manual crusher,working table, cleaning unit and crushing vessel stocker is carried outby the crushing vessel transferring unit. Therefore, the heavy crushingvessels are automatically transferred without using manual operation,but the operations of introduction and removal of samples and cleaningof the vessels are manually effected, whose manual operations arepreferable. Accordingly, the crushing operation of samples can becarried out in safety with high efficiency.

FIGS. 9 and 10 are plan and front views illustrating one example of theanalysis sample transferring apparatus together with a fluorescent X-rayanalyzing apparatus. In this embodiment, the analysis sampletransferring apparatus is provided between an automatic press 101 and afluorescent X-ray analyzing apparatus 102. The analysis sampletransferring apparatus comprises: a formed sample transferring unit 103for transferring and temporarily storing formed samples, a formed sampleloading and unloading unit 104 for loading and unloading a formed sampleinto and out of a predetermined holder and loading and unloading theloaded and unloaded holder into and out of a holder tray, formed sampledelivery unit 105 for transferring the formed samples between the formedsample transferring unit 103 and the formed sample loading and unloadingunit 104, a holder tray transferring unit 106 for transferring theholder tray to a predetermined position, and a standard sample storingand lifting unit 107.

In this embodiment, the formed sample 112, transferred to a formedsample removing opening 111 of the automatic press 101 by elevatingmeans (not shown), is supplied to a raillike pool 113 of the formedsample transferring unit 103 and are stored therein if required. Theformed sample 112 arrived at an end of the pool 113 is held by a formedsample delivery unit 105 and rotated under this condition into aposition shown by phantom lines in FIG. 9. In the formed sample loadingand unloading unit 104 at a position of the rotated formed sample 112,the formed sample 112 is loaded into the holder 115 previously arrangedin the holder tray 114 by a clamp built-in spindle (not shown). Afterloading formed sample 112 into six holders 115, the holder tray 114 istransferred by the holder tray transferring unit 106 to a predeterminedposition in front of a sample loader 116 of the fluorescent X-rayanalyzing apparatus 102. The holder 115 is loaded with the formed sample112 therein is supplied one by one to the fluorescent X-ray analyzingapparatus 102 to be analyzed. After analysis, the formed samples 112 arereturned together with the holders 115 to the holder tray 114 andfurther transferred to the formed sample loading and unloading unit 104by the holder tray transferring unit 106. The analyzed formed samples112 are removed one by one from the holder 115 by means of the formedsample loading and unloading unit 104. Thereafter, the formed samples112 are fed by the formed sample delivery unit 105 through introducingchute 17-1 or 17-2 into sample storing cases 118 and stored therein.

Before starting usual analyzing operations, the fluorescent X-rayanalyzing apparatus 102 must be calibrated with calibration curves orapparatus itself. For this purpose, the reference sample storing andlifting unit 107 (for storing reference samples) is provided in atransferring path of the holder tray 114 so that reference samples 119can be supplied to the fluorescent X-ray analyzing apparatus 102 as thecase may be. The reference sample storing and lifting unit 107 isconstructed such that eight trays 120, each supporting six referencesample at the most, can be accommodated therein.

FIGS. 11a 11b and 11c are sectional and bottom plan views of the holder115 and a sectional view of the clamp builtin spindle 121. FIG. 11aillustrates the holder 115 and the formed sample 112 therein. In moredetail, a holder body 122 is formed integrally with a mask 123 and aplastic insert 124 to form a holder body unit. A movable lock plate 125supporting thereon the formed sample 112, a spring 126 and a springanchoring member 127 form a locking unit. The locking unit is insertedinto the holder body unit so that pawls 129 of the lock plate 125 areurged against notches 128 of the holder body 122, thereby holding theformed sample 112 to the holder 115. As shown in FIG. 11b, the lockplate 125 is provided on its bottom with a clamp engaging portion 130and two position detecting apertures 131-1 and 131-2. The clamp built-inspindle 121 comprises movable clamp 133 and a diffused reflection typephotoelectric switch 134 arranged in a spindle member 132 as shown insection in FIG. 11c.

The loading and unloading operation of the formed sample 112 using theholder 115 and the clamp built-in spindle 121 will be explained. Theholder 115 supporting the analyzed formed sample 112 is transferred bythe holder tray 114 to the center of the formed sample loading andunloading unit 104 and stopped thereat. In this position, the clampbuilt-in spindle 121 is raised from below and once stopped immediatelybefore a tip end of the spindle 121 contacts the movable lock plate 125.At the same time, the spindle 121 is slowly rotated as a whole so that aposition at which the holder body 122 is to be clamped is determinedwith the aid of the photoelectric switch 134 and the position detectingapertures 131-1 and 131-2. Thereafter, the spindle 121 in its entiretysupporting on the tip end the holder 115, is further raised, while beingslowly rotated. The spindle 121 is then stopped at the position of theholder clamp mechanism of the formed sample loading and unloading unit104 to clamp the holder body 122. Under this condition, the clamp 133 inthe spindle 121 is actuated to disengage the pawls 129 of the movablelock plate 125 from the notches 128 of the holder body 122. Thereafter,the spindle 121 is lowered together with the lock plate 125 and theformed sample 112 thereon so that the formed sample 112 is exchangedwith a new formed sample 112 by means of the formed sample transfermeans 105. The new formed sample 112 is then accommodated in t he holderbody 122. The complete loading of the formed body 112 in the holder body122 is ascertained by detecting the positions of the pawls 129 of themovable lock plate 125 by means of the photoelectric switch 134.

As can be seen from the above explanation, the analysis sampletransferring apparatus, according to the invention, is capable ofautomatically transferring formed samples so that formed samples for theanalysis can be automatically transferred to a predetermined analyzingapparatus without requiring manual operation. Moreover, as the referencesample storing and lifting unit is added to the holder tray transferringunit, calibration lines or calibration of an analyzing apparatus inanalyzing various kinds of samples can easily be effected so thatprecise analyzing can be carried out.

FIG. 12 is a plan view illustrating one example of the fluorescent X-rayanalyzing system according to the invention. In this embodiment, asample is crushed to a predetermined grain size in an automatic crusher151 and the crushed sample is then transferred to an automatic press 153by a crushed sample transferring unit 152. The crushed sample is formedinto predetermined shapes such as disks in the automatic press 153, andthe formed samples are supplied by a formed sample supply unit 154 to afluorescent X-ray analyzing apparatus 155 through a partition wallseparating the fluorescent X-ray analyzing apparatus 155 and apretreating unit including an automatic crusher 151 and the automaticpress 153. The formed samples supplied to the analyzing apparatus 155are once stored if required and thereafter are loaded in a holder in asample loader 159 by means of a holder loading and unloading unit 158.Thereafter, the samples are set in the fluorescent X-ray analyzingapparatus 155 by an action of the sample loader 159 for carrying out theX-ray fluorescence analysis. Operations of the automatic crusher 151,crushed sample transferring unit 152, automatic press 153, formed samplesupply unit 154, sample transfer pooling unit 157, holder loading andunloading unit 158, sample loader 159 and fluorescent X-ray analyzingapparatus 155 are controlled by control means 160. The control means 160comprises usual computers.

FIGS. 13 and 14 are plan and side views illustrating an upperconstruction of the automatic crusher 151 in the fluorescent X-rayanalyzing system according to the invention. As shown in these drawings,at the upper portion of the automatic crusher, a first cup pooling unit171 and a sample introducing unit 172 are provided on a base 173 forselecting particular samples from various kinds of samples andintroducing them into the automatic crusher 151. In more detail, thefirst cup pooling unit 171 comprises sample racks 174-1 to 174-8, eachincluding ten sample cups 175. There are totally 80 sample cups 175.Before starting the operation, positions and kinds of the eighty samplecups are inputted into the control means 160, on the basis of whichinputted data the crushing is actually effected. The first cup poolingunit 171 is able to move in both directions as shown by an arrow so thata rack or rack 174-1 in this embodiment positioned at a rack movingposition a is transferred to a sample introducing position shown in thedrawing. The sample in the sample cup 175 at the sample introducingposition is held and transferred together with the sample cup 175 by acup grasping unit 176 of the sample introducing unit 172 in apredetermined order so as to be introduced into a sample introducingopening of the automatic crusher 151 by an action of the cup graspingunit 126.

The crushed samples are supplied from a sample exhaust opening 177 ofthe automatic crusher 151 to a crushed sample cup 179 of crushed samplepooling unit 178 as second cup pooling unit of the crushed sampletransferring unit 152 as shown in FIG. 14. The crushed sample cups 179are transferred in desired timing to a position of a cup loading andunloading unit 180 by means of the crushed sample pooling unit 178. Thecrushed samples are weighed by an electronic balance 186 if required.The cup 179 is held by the cup loading and unloading unit 180, while acup transferring unit 182 is transferred to the position of the cuploading and unloading unit 180. The cup 179 is held by grasping means183 of the unit 180 and then supplied to the automatic press 153.

If the sample is a ceramic, it must be crushed to a size of the order ofmean diameter of about 0.3 μm in order to effect the X-ray fluorescenceanalysis with high accuracy. In the present system, the sample is addedwith a crushing aid and crushed under a dried condition. The automaticcrusher 151 and the automatic press 153 may be commercially availableones. For example, Model HSM-F36 (HERZOG Company) and the like arepreferably used as the automatic crusher for the embodiment. Moreover,in the automatic press 153, supplied sample powder is pressed in apredetermined ring which can be loaded in a sample holder of thefluorescent X-ray analyzing apparatus 155 to form a formed sample 185which is removed through a formed sample removing opening 34. Theautomatic press 153 includes an analyzed sample supply means (not shown)for punching measured samples and recovering the forming rings.

Moreover, the fluorescent X-ray analyzing system includes an analysissample transferring apparatus. Such an apparatus is substantially thesame as that shown in FIGS. 9 and 10, and a holder and a clamp built-inspindle are also substantially the same as those shown in FIGS. 11a, 11band 11c.

The arrangement of the automatic crusher, automatic press andfluorescent X-ray analyzing apparatus is not limited to that shown inthe above embodiment. All that is required is an effective connection ofthese apparatuses.

The fluorescent X-ray analyzing system according to the invention usesthe automatic crusher capable of selecting various kinds of samples andcrushing them, so that various kinds of samples can be continuously andautomatically analyzed. Moreover, the crushed sample transferring unitand the formed sample supply unit connect between the automatic crusher,automatic press and fluorescent X-ray analyzing apparatus. Operations ofthese components are controlled by the control means. Therefore,automatization of the system and saving power can be accomplished.

It is further understood by those skilled in the art that the foregoingdescription is that of preferred embodiments of the disclosed inventionand that various changes and modifications may be made in the inventionwithout departing from the spirit and scope thereof.

What is claimed is:
 1. A method of pretreating a sample for X-rayfluorescence analysis comprising the steps of:adding a sample under anypowdery, granular or conglomerate conditions with graphite and a formingaid simultaneously or one after another; crushing the sample under adried condition; and press-forming the sample.
 2. A method as set forthin claim 1, wherein the forming aid is styrene-maleic acid copolymer. 3.A method as set forth in claim 1, wherein in the step of press-forming,material holding means is used.